Bridged polysilsesquioxanes BPs are an emerging group of organic-inorganic hybrid materials in which organic moieties are built into a siloxane matrix by hydrolytically stable covalent carbon-silicon bonds. The formation of these solids is kinetically controlled, i.e., all synthesis parameters that can influence the kinetics of the sol-gel process affect both physical and chemical properties of target materials. Structure-adsorption characteristics such as porosity, specific surface area, pore volume or surface composition are also easily modulated during sol-gel processing by a suitable choice of synthesis conditions. The possibility of tailoring the properties makes BPs potential candidates for adsorption applications – several works describing such attempts have appeared in the literature to date. In this paper, the synthesis strategy, creation of porosity and some examples of using BPs as adsorbents are briefly discussed.